| 摘要 |
Cross-linked polymerizable materials are produced by heating to at least 100 DEG C., with or without application of pressure, an interpolymer containing free carboxyl and nitrile groups attached to the same polymer chain, the ratio of carboxyl to nitrile groups being in the range of 1:10 to 10:1, the interpolymer being obtained by the interpolymerization of an alpha, beta ethylenically unsaturated carboxylic acid with an alpha, beta ethylenically unsaturated nitrile, with or without the addition of a third copolymerizable compound, the interpolymer containing at least 10 mols. per cent. of the unsaturated acid and unsaturated nitrile compounds in its structure. Unsaturated acids and nitriles specified are acrylic, methacrylic, crotonic, angelic, tiglic, cinnamic, chloracrylic, maleic, fumaric, mesaconic, and citraconic acids and the corresponding nitriles. Other polymerizable monomers specified are butadiene, vinyl formate, acetate, propionate, butyrate, stearate, benzoate, and crotonate, esters of allyl, methallyl, ethallyl, chlorallyl, crotonyl, and cinnamyl alcohols and but-1-ene-3-ol and pent-1-ene-3-ol with formic, acetic, lactic, butyric, glycollic, salicylic, oleic, benzoic, and phthalic acids, vinyl methyl, ethyl, isopropyl and butyl ketones, allyl substituted aldehydes and ketones, vinyl methyl, ethyl, isopropyl, butyl, phenyl, tolyl, naphthyl, vinyl, and propenyl ethers, allyl ethers, styrene, alpha methyl styrene, nuclear alkyl styrenes, ethyl acrylate, methyl methacrylate, ethyl chlormaleate, ethyl citraconate, vinyl chloride, N-vinyl urethanes, N-vinyl carbazole, N-vinyl pyrrole, N-vinyl piperidine, N-vinyl pyrollidone, and allyl substituted acetals and ketals. Polymerization may be carried out in bulk, in solution in a solvent such as acetone, or in aqueous emulsion containing a dispersing agent such as sodium lauryl sulphate, and may be effected with the aid of heat, ultra-violet light, and catalysts such as benzoyl peroxide, isopropylbenzene hydroperoxide, and, in aqueous emulsion, a mixture of potassium persulphate and sodium metabisulphite. When polymerizing in aqueous emulsion the mixture of monomers and catalyst may be added gradually to the reaction mixture as polymerization proceeds. The cross-linking of the interpolymers may be effected by conducting polymerization at temperatures above 100 DEG C., or by applying the heat treatment to the interpolymers after their preparation, preferably with the aid of an acidic catalyst such as phosphoric acid, ammonium chloride, ammonium phosphate, aluminium chloride, zinc chloride, p-toluene sulphonic acid, beta-camphoryl sulphonic acid, trichloracetic acid, and cetostearyl hydrogen phthalate. The process may be applied to the cross-linking of mouldings and coatings, and also to fibres, as exemplified by the insolubilization of a pre-stretched fibre made from an acrylonitrile/acrylic acid/styrene terpolymer by heating at 130 DEG C. |
